Polymerizable and polymerized compositions comprising an n-vinyl-n-alkyl guanidine



Patented Mar. 2, 1954 {POLYTME'RI'ZA'BLE TA'ND FPOLYM ERIZED= GOM- nosrrIoNs @coMgRIsING N VINYL-N- ,{ALKYLQUANIDINE John Ai Pricefstamford ican Cyanam-id Com corporationofiMaine Conrn, assignor toAmerpany, New"-York, N. Y., a

'ltlognrawing. Application October. 2.4, 1951,

QSeria No. 253,006

This invention relates to theproductionof new materials having valuable and characteristic properties that make them especially suitable for use in industry,-for example in molding,-casting, coating, electrically insulating-and adhesive applications, and for other'purposes. More particularly the invention isconcerned with polymerizable compositions comprising} byweight (1') from 1% to "75% (about*1-% t -about 75%) of an N-vinyl-N-alkyl -g uani d -ine,- e. g., N -vinyl-N -ethyl guanidine, and (2);'fromf25%'to 99%-- (about 25% to-about 99%) ofa-compound which is diiferent from the=confipound of l) is copolymerizable therewith-and-Which-centains a CH2=C grouping or a plurality of CH2=0 'groupings, -e. -g., styrene, -acrylonitrile, ethyl -'acrylate, glycidyl methacrylate, vinyl ;-acetate, diallyl phthalate, divinyl benzene; etc; ora-pluralityof such com pounds. The scope of the invention also includes products comprising :the 'polymerized composition obtained by polymerization of the aforementioned polymerizable'composition,as-wellasmethod features whereby new-- and-useful 'synthetic compositions.areproduced.

The N-vinyl N alkyLguanidines used impracticing the present inventionecanube represented bythe formula Alkyl "NB cH2=c {1'1 The alkyl radical in themabovejormulacan be, for instance, methyl,.,ethyl pl opyl, eisopropyl, n-butyl, isobutyl, sec.-butyl,'tert.- butyl, amyl, isoamyl, hexyl to octadecyh inclusive, cyclopentyl, cyclohexyl, cycloheptyl, .benzyl, phenylethyl, phenylpropyl, etc.

.The aforementioned N.-v,inyl -'N all;yl I guanidines are believed to be new hemicalcompou d and are more -fully described and *claimed ;as such, as well as a mjethod of"; preparing "the same, in the copending application of Ingenuin'I-Iechenbleikner and'Dona1d'W,-- g iser, Serial"l T;i253,004, filed concurrently-herew-ith.

fl't' is oneo'fthe primary objects of the present invention to prepare-'a- -new blass of copolymers or interpolymers for use in'-irfdust-ry.

Still another and important object-ef-"the -in vention Y is the production ofcopolymers or 1 interpolymers ofa'basic monomer,Moreparticularly an N-vinyl-N-alkylguanidine and one or more non-basic 'monomers, -e.;+'g., acnylonitrile, which polymerization 'i-pro'ducts are more readily dye'd, especiallwwith -acid dyesathan polymersiof acrytonitrile or other non-basic -monomer alone, or than many ofthe previously known or suggested copolymers of (I) acrylonitrile( rother nonbasic monomer) and (2) another different monomer or; monomers.

Another object of the invention is to prepare copolymers which can be spun or otherwise shaped to formffilaments, tape, ribbon s, tubes, rods, sheets, etc., andthe ,shaped articles then dyed either before or after having fbeen oriented or treatedto improve their useful properties.

- Other objects ofthe invention will be apparent to those skilled inthe "artfrom the description and examples'which follow.

"The foregoing objectsare attainad bycopblymerization of an N -vinyl -N-alkyl guanidine with one or -more other comonomers which are copolymerizable therewith, 1more particularly such comonomers which containeither a-single or a plurality of CH2=C groupings,1 using-by weight, from about, 1% to about'75%, preferably" (for the usual applicationsfifrom about 17orj2%"t0 ;abQ .1t 15 or i 20%, of an gN vinyl-N-alkyl guanidine, e. g., N -vinyl-N -ethyl guanidine, and 'from ;about 25% to about 99%, preferably {for the usual a plications) from about :98 1or "99% *to about 'or of a comonomer fiorcor'nonomers) containing one 'or,more "CI-I2=C groupings. Heat,'light or heatand light can be used to effect orto accelerate polymerization of the mixture of comonomers, although under; such conditions the ratewofpolymerization in, some cases may be relatively slow, as for instance when .the N- vinyl -N-alkyl. guanidine ,constitutes ,only asm'all amount (e. g., .1 to 5%) of thenmixtureiof. gomonomers and the: other. comonomer .normally has a slow polymerization rate. ;lllence,,it; is usually preferred .to accelerate the polymerization byemploying a -polymerizationecatalystaccompanied byheat, light or heat andl ig ht. ther details of polymerization conditions rate given hereinafter.

Examples-of monomers (comonomers) pent-aining;a CH2=C grouping -;that icanibe -'copolymerized with an :N-vinyl-N-allgyl -guan-idine;-;in the :weight proportions;hereinbefore;=:mentioned, n ly r l ral yv(tw ee, fo r-101 any 5d-- sired number) 1 thereof; the latterxoftengbeingidesirable in" order to improve the ;compatibility and copolymerization characteristics of ;:'*-.the-: ;mixt;ure

of:;monomers :and ;;to.;obtain new .-..and valuable copolymers; having: the -'particu-lar prcipertiesidesired for a a particular service application, ware suchunonomersasstheunsaturated alcohol esters, moreezparticularly :thezallyl, eimethallylacrotyl ,-::1

etc.), crotonic, oxalic, malonic, succinic, glutaric,

adipic, pimelic, suberic, azelaic, sebacic, fumaric, citraconic, mesaconic, itaconic, acetylene dicarboxylic, aconitic, benzoic, phenylacetic, phthalic, terephthalic, benzoylphthalic, etc., acids; the saturated monohydric alcohol esters, e. g., the methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, amyl, etc., esters of unsaturated aliphatic monobasic and polybasic acids, illustrative examples of which appear above; vinyl cyclic compounds (including monovinyl aromatic hydrocarbons), e. g., styrene, mand p-chlorostyrenes, -bromostyrenes, -fiuorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes, the various polysubstituted styrenes such, for example, as the various di-, triand tetra-chlorostyrenes, -bromostyrenes, -fiuorostyrenes, -methylstyrenes, -ethylstyrenes, -cyanostyrenes, etc., vinyl naphthalene, vinylcyclohexane, vinyl furane, vinyl pyridine, vinyldibenzofuran, divinyl benzene, trivinyl benzene, allyl benzene, diallyl benzene, N-vinyl carbazole and the various allyl cyanostyrenes; the various alpha-substituted styrenes and alpha-substituted ring-substituted styrenes, e. g., alphamethyl styrene, alpha-methyl-para-methyl styrene, etc.; unsaturated ethers, e. g., ethyl vinyl ether, diallyl ether, ethyl methallyl ether, etc.; unsaturated amides, for instance N-allyl caprolactam, acrylamide, and N-substituted acrylamides, e. g., N-methylol acrylamide, N-allyl acrylamide, N-methyl acrylamide, N-phenyl acrylamide, etc.; unsaturated ketones, e. g., vinyl ketone, methyl allyl ketone, etc.; methylene malonic esters, e. g., methylene methyl malonate, etc.; butadienes, e. g., 1,3-butadiene, Z-chlorobutadiene, etc.; unsaturated polyhydric alcohol (e. g., butenediol, etc.) esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids, illustrative examples of which appear above; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, glycidyl allyl phthalate, etc.

. Other examples of monomers that can be copolymerized with an N-vinyl-N-alkyl guanidine to produce my new copolymer compositions are the vinyl halides, more particularly vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide, and the various vinylidene compounds, including the vinylidene halides, e. g., vinylidene chloride, vinylidene bromide, vinylidene fluoride and vinylidene iodide, other comonomers being added if needed in order to improve the compatability and copolymerization characteristics of the mixed monomers.

Other and more specific examples of monomeric materials which can be mixed or blended with an N-vinyl-N-alkyl guanidine in the aforementioned proportions, and the resulting homogeneous or substantially homogeneous, polymerizable composition then polymerized, as hereinafter more fully described, to yield new and valuable copolymer compositions are the allyl compounds which are difierent from the basic monomer used in practicing the present invention and especially those which have a boiling point of at least about 60 C. Of the monomeric materials which can be used the allyl esters form a large class. The reactive allyl compounds employedare 4 preferably those which have a high boiling point such, for example, as diallyl maleatc, diallyl fumarate, diallyl phthalate, diallyl succinate, etc. Other allyl compounds which are not necessarily high boiling also may be used.

Additional examples of allyl compounds, and of other compounds containing one or more CH2=C groupings that can be used in producing the new and useful copolymers or interpolymers of'the present invention, are given in, for example, Drechsel and Padbury Patent No. 2,550,652 dated April 24, 1951, and especially in that portion thereof with particular reference to monomers used'in forming copolymers with diallyl cyanamide.

Among the comonomers which are preferred for use in carrying my invention into effect are the vinyl compounds which are different from the primary basic monomer employed, including the vinyl aromatic compounds, more particularly the vinyl aromatic hydrocarbons (e. g., styrene, the various dialkyl styrenes, etc), and the vinyl aliphatic compounds, e. g., acrylonitrile, acrylamide, etc., and other and difierent compounds containing a CH2=C grouping, e. g., isopropenyl toluene, the various substituted acrylonitriles (e. g., methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, etc.) the various substituted acrylamides (e. g., methacrylamide, ethacrylamide, the various N-substituted acrylamides and alkacrylamides, ,for instance N-methylol acrylamide, N-monoalkyl and -dialkyl acrylamides and methacrylamides, e. g., N-monomethyl, -ethyl, -propyl, -butyl, etc., and N-dimethyl, -ethyl, -propyl, -butyl, etc., acrylamides and methacrylamides, N-monoaryl and -diary1 acrylamides and alkacrylamides, e. g., N monophenyl and -diphenyl acrylamides and methacrylamides, etc), vinyl esters, e. g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl acrylate, vinyl methacrylate, etc., esters of an acrylic acid (including acrylic acid itself and the various alpha-substituted acrylic acids, e. g., methacrylic acid, ethacrylic acid, phenylacrylic acid, etc), more particularly the alkyl esters of an acrylic acid, e. g.-, the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.butyl, tert.-butyl, amyl, hexyl, heptyl, octyl, decyl, dodecyl, etc., esters of acrylic, methacrylic, ethacrylic, phenylacrylic, etc., acids, including the alkyl acrylates containing not more than four carbon atoms in the alkyl grouping, examples oi which are given above, as well as other vinyl aromatic and vinyl aliphatic compounds, and other compounds containing a CH2=C grouping.

Any suitable means may be used in efiecting polymerization of the admixture of the N-vinyl- N-alkyl guanidine and one or more other monomore which are copolymerizable therewith. As has been mentioned hereinbefore heat or light or both, with or without a polymerization catalyst, can be used. Ultraviolet light is more efiective than ordinary light. Preferably a polymerization catalyst is employed. Any of the poly merization catalysts which are suitable for use in polymerizing compounds containing an ethylenically unsaturated grouping, specifically a vinyl grouping, can be employed. Among such catalysts are the inorganic peroxides, e. g., hydrogen peroxide, barium peroxide, magnesium peroxide, etc., and the various organic peroxy catalysts, illustrative examples of which latter are: the dialkyl peroxides, e. g., diethyl peroxide, dipropyl peroxide,rdilauryl peroxide, dioleyl peroxide, distearyl. peroxide. di-itert-buty i pe x de... an

di-..(tert.-amy1 peroxide. such peroxides often being des gnated as ethyl, nropyl. Iauryl, cleyl, stearyl, tert.-butyl and tert.-amyl peroxides; the alkyl hydrogen peroxides, e. g., tert.-butyl hydrogen peroxide (tert.-buty1 hydroperoxide), tert.-amyl hydrogen peroxide (tert.-am yl hydroperoxide), etc.; symmetrical diacyl peroxides, for instance peroxides which commonly are known under such names as acetyl peroxide, propionyl peroxide, lauroyl peroxide, succinyl peroxide, phthaloyl peroxide, benzoyl peroxide, etc.,' fatty oil acid peroxides, e. g., coconut oil acid peroxides, etc.; unsymmetrical or mixed diacyl peroxides, e. g'., acetyl benzoyl peroxide, propionyl benzoyl peroxide, etc.; terpene oxides, e. g., ascaridole, etc.; and salts of inorganic peracids, e. g., ammonium persulfate, sodium persulfate, potassium persulfate, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium perphosphate, potassium perphosphate, etc. Other examples of organic peroxides and of other catalysts that can be employed are given in the aforementioned Drechsel and Padbury Patent No. 2,550,652.

The concentration of the catalyst employed is usually small, that is, for the preferred catalysts from, by weight, about 0.5 or 1 part of catalyst per thousand parts of the polymerizable composition to be polymerized to about 3 or 4- or more parts of catalyst per 100 parts of the mixture of comonomers. If an inhibitor of the .kind hereinafter mentioned be present, larger amounts of catalyst may be necessary according to the concentration of the inhibitor.

If desired, the mixed monomers can be polymerized in emulsion or in solution state to yield a copolymer. In the latter case, various inert organic solvents may be employed, depending upon the particular comonomer used, c. g., toluone, xylene, dioxane, ethers (e. g., dibutyl ether), esters (e. g., butyl acetate), chlorobenzene, ethylene dichloride, ketones (e. g methyl ethyl ketone), tertiary alcohols, for instance tertiary-butyl alcohol, tertiary-amyl alcohol, tertiary-hexyl alcohol, etc., as well as others. When the reaction is effected in solution state, then a temperature at or approaching the boiling temperature of the solution generally is used.

The polymerization also. can be effected by conventional bulk polymerization technique, in the presence or absence of a solvent capable of dissolving the monomeric mixture and in which the latter preferably is inert; or in solution in a solvent in which the monomeric mixture is soluble but the copolymer is insoluble; or by conventional bead polymerization methods. The polymerization of the mixture of monomers can be effected by a continuous process as well as by a batch operation.

The temperature of polymerization of the polymerizable composition, at atmospheric or slightly above atmospheric pressure and in the presence or absence of a polymerization catalyst, can be varied over a wide range, up to and including or slightly above the boiling point (at atmospheric pressure) of the monomeric mixture (or of the lowest boiling component thereof), but in all cases is below the decomposition temperature of the monomericv materials. In most cases the polymerization temperature will be within the range of C. to 150 C. more particularly within the range of C. or 30 C. (ordinary room temperature) to 130 C., depending upon the particular mixture o mgilom rs mployed. the part cular 31 911351 4 if any, used. the rapidity of polymerization want .ed, and other influencin factors. With certain catalysts, more particularly strong acidic polymerization catalysts such, for instance. as gaseous boron trifluoride-ethyl ether complex, concentrated sulfuric acid, anhydrous aluminum chloride, etc., a substantially lower polymerization temperature often advantageously may be used, e. g., temperatures ranging between .80 C. and 0 C. or 10 C. At the lower temperatures below the solidification point of the monomeric mixture (or components thereof), polymerization is efiected while the mixture of monomers is dissolved or dispersed in a solvent or dispersion medium which is liquid at the temperature of polymerization. Or, if desired, the monomeric mixture, that is, the polymerizable composition, can be polymerized in dissolved or dispersed state at temperatures above its solidification point or above the solidification point of the polymerizable components thereof. The copolymer can be separated from the liquid medium in which copolymerization was effected by any suitable means, e. g., by filtration, centrifuging, solvent extraction, etc.

In some cases it may be desirable to incorporate into the polymerizable composition an inhibitor which is adapted to inhibit copolymerization of the individual monomers present in the composition. When it is desired to use the inhibitcr-modified composition, a catalyst is added in an amount suflicient to promote the polymerication reaction and to yield a copolymer. Any suitable inhibitor can be used, e. g., tannin, phencl, resorcinol, hydroquinone, ascorbic acid, isoascorbic acid, phenyl-a-naphthylamine, N,N- di-2-naphthyl-p-phenylenediamine, certain cupric salts, e. g., cupricacetate, etc. The amount of the polymerization inhibitor may be considerably varied, but ordinarily it is employed in an amount not exceeding 3%, generally less than 1 by weight of the monomer or mixture of comonomers, e. g., from 0.01% to 0.5% or 0.6% by weight thereof.

In order that those skilled in the art may better understand how the present invention can be carried into effect, the following examples are given by way of illustration and not by way of limitation. All parts and percentages are 'by weight.

Example 1 This example illustrates the preparation of homopolymeric acrylonitrile, which is subsequently employed in comparative tests with certain of the copolymers of the present'invention.

A reaction vessel, equipped with a stirrer, refiux condenser, thermometer and gas-inlet tube, is placed in a constant-temperature bath which is maintained at 35 C. To the vessel is added a solution of 53.0 parts of acrylonitrile, 900 parts. of distilled water and 0.29 part of sulfuric acid. The pH of the initial solution is 3.1. A rapid stream of pre-purified nitrogen is passed over'the: surface of the solution for 30 minutes. The nitrogen flow is then reduced to about one bubble per second. A reduction-oxidation catalyst system (redox system) consisting of 1.71 parts of ammonium persulfate and 0.71 part of sodium meta-bisulfite, each dissolved in 50 parts of water, is then added. The. solution first becomes cloudy at the end of 3- minutcs, and the polymerization is fairly exothermic for the first half hour. The. olymerization is continuedifor a total of 4 hours at 35 0.. The polymer is collected on a, Biichner. funnel. and wajfihedi with; 1.000,; parts, oi; distilled water followed by about 160 parts of methanol.

The polymer is dried in an oven at 70 C. for

about 16 hours. The yield of dry polyacrylonitrile, which is white, amounts to 48 parts.

Example 2 A reaction vessel, equipped with a stirrer, reflux condenser, thermometer and gas-inlet tube is placed in a constant-temperature bath which is maintained at 60 solution of 71.25 parts of acrylonitrile, 3.75 parts of N-vinyl-N-ethyl guanidine and 1000 parts of distilled water. A rapid stream of pre-purified nitrogen is passed over the surface of the solution for 30 minutes. The nitrogen flow is then decreased to one bubble per second. To the vessel is now added a suitable amount of a polymerization catalyst, more particularly 1.5 parts of a eazodiisobutyronitrile. The polymerization is carried out for 4 hours at 60 C. The copolymer is collected on a Biichner funnel, washed with 2,000 parts of deionized water and dried in an oven at 70 C. for about 16 hours. The yield of dry, white copolymer of acrylonitrile and N- vinyl-N-ethyl guanidine amounts to 59 parts.

Example 3 Exactly the same procedure is followed as described under Example 2 with the exception that instead of 3.75 parts of N-vinyl-N-ethyl guanidine there is used 3.75 parts of N-vinyl-N-methyl guanidine. A good yield of a solid copolymer of acrylonitrile and N-vinyl-N-methyl guanidine is obtained. A portion of the dry copolymer is used in the dye tests described in a later example.

Example 4 Same as in Example there are used 67.5 parts instead of 71.25 parts of acrylonitrile, 7.5 parts of N-vinyl-N-n-butyl guanidine instead of 3.75 parts of N-vinyl-r ethyl guanidine, and 2 parts instead of 1.5 parts of 1. -azodiisobutyronitrile;; also, the time of polymerization is 8 hours instead of 4 hours at 60 C. A portion of the resulting solid copolymer of acrylonitrile and N-vinyl-N-n-butyl guanidine is employed in the dye tests described in a later example Example 5 In this example, too, exactly the same procedure is followed as described under Example 2 with the exception that there are used 73.5 parts instead of 71.25 parts of acrylonitrile and 1.5 parts of N-vinyl-N-cyclohexyl guanidine in place of 3.75 parts of N-vinyl-N-ethyl guanidine. A good yield of a solid copolymer of acrylonitrile and N-vinyl-N-cyclohexyl guanidine is obtained. A portion of the dry copolymer is employed in the dye tests described in a later example.

Example 6 Same as in Example 2 with the exception that there are used 63.75 parts instead of 71.25 parts of acrylonitrile, 11.25 parts of N-vinyl-N-benzyl guanidine in place of 3.75 parts of N-vinyl-N- ethyl guanidine, and 3.5 parts instead of 2 parts of .-azodiisobutyronitrile; also, the time of polymerization is 12 hours at 65 C. instead of 4 hours at 60 C. A portion of the result ng solid copolymer of acrylonitrile and N-vinyl-N-benzyl guanidine is employed in the dye tests described in a later example;

In the same manner described in the preceding paragraph, a. copolymer of mixed monomers consisting of from about 1% to about 20% of an N -vinyl-N-alkyl guanidine, e. g., N-vinyl-N-ethyl guanidine, and from about 80% to about 99% or. vdifferentvimrl compound-, e. 9., acrylonitrile,

2 with the exception that C. To the vessel is added 2.

more particularly from about 2% to about 15% byweight of N-vinyl-N-ethyl guanidine and the remainder acrylonitrile, can be produced.

Example 7 A tripolymer of (1) a vinyl aliphatic compound, specifically acrylonitrile, (2) an alkyl ester of an acrylic acid, more particularly such an ester containing not more than 4 carbon atoms in the alkyl grouping, and specifically ethyl acrylate, and (3) an N-vinyl-N-alkyl guanidine, specifically N-vinyl-N-ethyl guanidine, is produced by following exactly the same procedure given under Example 2 with the exception that there are used 67.5 parts instead of 71.25 parts of acrylonitrile; 3.75 parts of methyl acrylate in addition to 3.75 parts of N-vinyl-N-ethyl guanidine; and 2 parts instead of 1.5 parts of a,a'- azodiisobutyronitrile; also the time of polymerization is 8 hours instead of 4 hours at 60 C. A portion of the resulting solid copolymer of acrylonitrile, methyl acrylate and N-vinyl-N-ethyl guanidine is employed in the dye tests described in the folowing example.

Example 8 Samples of the homopolymeric acrylonitrile of Example 1 and of the copolymers of Examples 2 to 7, inclusive, are subjected to the following dye test:

A sample (5 parts) of the dry polymer or copolymer is added to a dye bath consisting of 500 parts of an aqueous solution containing 0.2 part of concentrated sulfuric acid, 1 part of sodium sulfate and 0.2 part of Calcocid Alizarine Blue SAPG (Color Index No. 1). The dye bath is boiled for 30 minutes, after which the polymerization product is filtered off and washed with hot water until the water is free of dye. The copolymers of Example 2 to 7, inclusive, are dyed blue, the intensity being, in general, directly proportional to the percentage of N-vinyl-N-alkyl guanidine used in forming the copolymer; that is, copolymers containing the higher content of the N-vinyl-N-alkyl guanidine compound yield, in general, the deeper dyeings. In marked contrast, the homopolymeric acrylonitrile of Example 1 fails to absorb any dye. The advantage of modifying an acrylonitrile polymerization product by replacing a part (c. g., from about 1.0% to about 15 or 20% or more, still more particularly from 2% to-5 or 10%) of the initial acrylonitrile with an N-vinyl-N-alkyl guanidine thereby to obtain a copolymeric acrylonitrile substance of improved dyeability is therefore quite apparent.

Example 9 To a. reaction vessel equipped as in Example 2 are charged 5 parts N-vinyl-N-ethyl guanidine, 45 parts ethyl acrylate, 200 parts water, 2 parts of an emulsifying agent, specifically sodium lauryl sulfate, and 0.5 part ofan organic peroxide polymerization catalyst, specifically benzoyl peroxide. The emulsion is stirred and maintained at 60 C. for 6 hours. At the end of the polymerization period the resulting copolymer of ethyl acrylate and N-vinyl-N-ethyl guanidine is precipitated by adding a small amount or" aluminum sulfate to to the emulsion. The precipitated copolymer is then filtered ofi and dried. The dried copolymer can be used as a modifier of homopolymeric acrylonitrile to improve the dyeability of the latter, especially with respect to acid dyes.

Example 10 Exactly the same procedure is followed as described under Example 9 with-the exception that 45 parts of styrene is used instead of 45 parts of ethyl acrylate, and the time of polymer ization is 8 hours instead of 6 hours. The resulting copolymer of styrene and N-vinyl-N-ethyl guanidine is isolated and dried as in Example 9. This copolymer, alone or admixed with dyes, fillers, stabilizers, or other additives, is suitable for use in the production of molding compositions and molded articles of various kinds.

Example 11 To a reaction vessel equipped as in Example 2 are charged 5 parts N-vinyl-N-ethyl guanidine, 5 parts vinyl acetate, 190 parts water and 0.4 part of ammonium persulfate. The resulting solution is maintained at 100 C. for 8 hours. At the end of the reaction period the precipitated copolymer of vinyl acetate and N-vinyl-N-ethyl guanidine is filtered off and dried. This copolymer may be used as a component of coating and impregnating compositions or as a modifier of other synthetic resins.

Example 12 To a reaction vessel equipped as in Example 2 are charged 2.5 parts N-vinyl-N-ethyl guanidine, 7.5 parts methyl methacrylate, 40 parts water, 0.5 part sodium lauryl sulfate and 0.2 part of potassium persulfate. The emulsion is stirred and maintained at 100 C. for 6 hours. At the end of the reaction period the emulsion is broken by the addition of a small amount of aluminum sulfate, e. g., an aqueous solution containing 0.2 part of aluminum sulfate, after which the precipitated copolymer of methyl methacrylate and N-vinyl-N-ethyl guanidine is filtered off and dried. This copolymer, with or without dyes, fillers or other additives, is suitable for use as a molding composition, or as a component of such compositions, from which molded articles of various shapes are produced by molding under heat and pressure.

Although the new copolymers of this invention are particularly useful in the formation of fibers or filaments which are more amenable to dyeing than homopolymeric acrylonitrile, they also have numerous other applications in the plastics and coating arts. For instance, with or without a filler or other additive, they may be used as molding compositions (or as components of molding compositions) from which molded articles are produced by molding the compositions under heat and pressure, e. g., temperatures of the order of 130 C. or 140 C. to 200 C. and under pressures up to 10,000 pounds or more per square inch. Among the fillers that can be employed in the production of molding compositions are alpha-cellulose pulp, asbestos fibers, cotton flock, chopped cloth cuttings, glass fibers, wood flour, antimony oxide, titanium dioxide, sand, clay, mica dust, diatomaceous earth, etc.

The polymerizable compositions of my invention can be used in the production of castings of any desired shape or size; as adhesives; in the treatment of paper or paper stock; in coating compositions; and for various other purposes. The copolymer can be formed in situ after application of the monomeric mixture to the base material to be coated, impregnated or otherwise treated.

Fibers can be produced from the copolymers of the present invention in the manner described in, for example, Patents 2,558,730, -'731 and -'733 with particular reference to the production of 10 a molecularly oriented fiber from homopolymeric or copolymeric acrylonitrile. The unoriented and oriented fibers produced from my new copolymers are readily dyed, especially with an acid dye, while the fiber is in either a gel (e. g., hydrogel or aquagel) or a'dry state.

The new materials (polymerizable compositions and polymerization products) of this invention have numerous other uses, for exampie uses such as are given in the aforementioned Drechsel and Padbury Patent No. 2,550,652.

I claim:

1. A polymerizable composition comprising, by weight, (1) from 1% to 75% of an otherwise unsubstituted N-vinyl-N -a1kyl guanidine and (2) from 25% to 99% of a compound which is different from the compound of (1), is copolymerizable therewith through the N-vinyl grouping of said guanidine, and which contains a CH2=C grouping.

2. A product comprising a copolymer which the polymerized composition of claim 1.

3. A composition comprising a copolymer of copolymerizable ingredients including, by weight, (1) from 1% to 20% of an otherwise unsubstituted N-vinyl-N-alkyl guanidine and (2) from 80% to 99% of a different vinyl compound which is copolymerizable with the said guanidine through the N-vinyl grouping thereof.

4. A composition as in claim 3 wherein the N-vinyl-N-alkyl guanidine is N-vinyl-N-ethyl guanidine.

5. A composition as in claim 3 wherein the vinyl compound of (2) is a vinyl aromatic compound.

6. A composition as in claim 5 wherein the vinyl aromatic compound is a vinyl aromatic hydrocarbon.

7. A composition as in claim 6 wherein the vinyl aromatic hydrocarbon is styrene.

8. A composition as in claim 3 wherein the vinyl compound is a vinyl aliphatic compound.

9. A composition as in claim 8 wherein the vinyl aliphatic compound is acrylonitrile.

10. A composition as in claim 8 wherein the vinyl aliphatic compound is an alkyl ester of an acrylic acid.

11. A composition as in claim 10 wherein the alkyl ester is an alkyl acrylate containing not more than 4 carbon atoms in the alkyl grouping.

12. A copolymer of mixed monomers consisting of from about 2% to about 15% by weight of N-vinyl-N-ethyl guanidine and the remainder acrylonitrile.

13. The method of preparing a new synthetic composition which comprises polymerizing, with the aid of a polymerization catalyst, a polymer izable mixture containing, by weight, (1) from 1% to 75% of an otherwise unsubstituted N- vinyl-N-alkyl 99% of a compoundwhich is different from the compound of (1), is copolymerizable therewith through the N-vinyl grouping of said guanidine, and which contains aCHz=C grouping.

JOHN A. PRICE.

References Cited in the file of this patent FOREIGN PATENTS Country Date Great Britain May 5, 1939 OTHER REFERENCES Number guanidine and (2) from 25% to 

1. A POLYMERIZABLE COMPOSITION COMPRISING, BY WEIGHT, (1) FROM 1% TO 75% OF AN OTHERWISE UNSUBSTITUTED N-VINYL-N-ALKYL GUANIDINE AND (2) FROM 25% TO 99% OF A COMPOUND WHICH IS DIFFERENT FROM THE COMPOUND OF (1), IS COPOLYMERIZABLE THEREWITH THROUGH THE N-VINYL GROUPING OF SAID GUANDINE, AND WHICH CONTAINS A CH2=C< GROUPING. 